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Formation, reactivity, and properties of nondative late transition metal-oxygen and -nitrogen bonds

journal contribution
posted on 2023-06-07, 23:22 authored by J Robin Fulton, Andrew W Holland, Daniel J Fox, Robert G Bergman
Complexes containing bonds between heteroatoms such as nitrogen and oxygen and "late" transition metals (i.e., those located on the right side of the transition series) have been implicated as reactive intermediates in numerous important catalytic systems. Despite this, Our understanding of such M-X linkages still lags behind that of their M-H and M-C analogues. New synthetic strategies have now made possible the isolation and study of a variety of monomeric late-metal alkoxide, aryloxide, and amide complexes, including parent hydroxide and amide species. The heteroatoms in these materials form surprisingly strong bonds to their metal centers, and their bond energies do not necessarily correlate with the energies of the corresponding H-X bonds. The M-X complexes typically exhibit nucleophilic reactivity, in some cases form strong hydrogen bonds to proton donors, and even deprotonate relatively weak acids. These observations, as well as thermodynamic investigations, suggest that late metal - heteroatom bonds are strongly polarized and possess significant ionic character, properties that play an important role in their interactions with organic compounds.

History

Publication status

  • Published

Journal

Accounts of Chemical Research

ISSN

0001-4842

Issue

1

Volume

35

Page range

44-56

Pages

13.0

Department affiliated with

  • Chemistry Publications

Notes

Times Cited: 90 Invited review. JRF organized review summarizing 15 years worth of research. Wrote 50% of article, with AWH and DJF contributing the rest. Edited by RGB.

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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